旋转提拉法提纯铟过程中的杂质迁移规律

Migration Behavior of Impurities during Indium Purification by Czochralski Method

摘要

为揭示旋转提拉法提纯铟过程中杂质的迁移规律,以Fe、Cu、Zn、Sn为典型杂质,系统研究了拉速与转速对其有效分配系数 K_eff 的影响.基于B-P-S模型计算了不同拉速(15~100 mm/h)和转速(1~10 r/min)下的 K_eff,并采用自主研制的真空旋转结晶炉开展单一变量提纯实验,通过GD-MS和SEM-EDS分别测定晶体中的杂质含量及观察微观形貌.理论计算表明,转速从1 r/min增至10 r/min时,Fe、Cu、Zn、Sn的K_eff 分别从0.338、0.315、0.844、0.893降至0.121、0.128、0.584、0.830;拉速从15 mm/h增至100 mm/h时,四种杂质的 K_eff 均增大,且低 K₀ 杂质对拉速更敏感.实验结果与理论趋势一致:拉速升高使Fe、Cu、Zn含量显著增加,Sn含量略有下降.SEM-EDS显示晶体尾部呈“中心—边缘”分区结构,中心为高纯铟(In>99.99%),边缘富集Fe、Cu、Zn、Sn;转速提高使富集区宽度减小约50%,证实了转速对溶质边界层厚度的调控作用.综上,本文验证了B-P-S模型在铟提纯中的适用性,揭示了旋转强迫对流对杂质分凝的关键调控机制.工艺优化建议:对Fe、Cu等低K₀杂质,宜采用低拉速(≤30 mm/h)配合高转速(≥10 r/min);对Sn等高K₀杂质,需结合其他提纯手段.

Abstract

To reveal the migration rules of impurities during the purification of indium by the Czochralski method,this study systematically investigated the effects of pulling rate and rotation rate on the effective distribution coefficients (K_eff ) of typical impurities including Fe,Cu,Zn,and Sn.The K_eff values at different pulling rates (15-100 mm/h) and rotation rates (1-10 r/min) were calculated based on the B-P-S model.Furthermore,single-variable purification experiments were carried out using an independently developed vacuum rotary crystallization furnace.The impurity contents in the crystals were determined by GD-MS,and the micro-morphologies were observed by SEM-EDS.Theoretical calculations showed that as the rotation rate increased from 1 r/min to 10 r/min,the K_eff of Fe,Cu,Zn,and Sn decreased from 0.338,0.315,0.844,and 0.893 to 0.121,0.128,0.584,and 0.830,respectively.When the pulling rate increased from 15 mm/h to 100 mm/h,the K_eff of all four impurities increased,and the lower-K_eff impurities were more sensitive to the pulling rate.The experimental results were highly consistent with the theoretical trends:a higher pulling rate significantly increased the contents of Fe,Cu,and Zn,while the Sn content slightly decreased.SEM-EDS results showed a “center-edge” zonal structure at the crystal tail,where the center was high-purity indium (In>99.99%),and the edge was enriched with Fe,Cu,Zn,and Sn.Increasing the rotation rate reduced the width of the enrichment zone by about 50%,confirming the key regulatory role of rotational forced convection on the solute boundary layer thickness.In summary,this study validated the applicability of the B-P-S model in indium purification and revealed the critical mechanism of the effect of rotational forced convection on impurity segregation.Process optimization suggestions:for low-K₀ impurities such as Fe and Cu,low pulling rates (≤30 mm/h) combined with high rotation rates (≥10 r/min) are recommended;for high-K₀ impurities such as Sn,additional purification methods should be combined.

关键词

旋转提拉法 / 高纯铟 / 晶体生长 / 界面动力学

Key words

Czochralski method / high-purity indium / crystal growth / interface dynamics

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基金资助

国家自然科学基金地区科学项目(202202AB080018)